Process of esterifying aldehydes



Patented Apr. 9, 1929.

UNITED STATES PATENT OFFICE.

JACQUES SCHALCH AND JOHN W. OLSON, OF CHICAGO, ILLINOIS, ASSIGNOBS 'I'O VAN SCHAACKBROS. CHEMICAL WORKS, INC., OF CHICAGO, ILLINOIS, A CORPORATION or ILLINOIS.

No Drawing.

Our invention relates to a process of esteritying aldehydes.

It is known that acetaldehyde 1n the presence of aluminum ethoxide may react with of our invention follows. A solution of 9 g. aluminum ethoxide that has been made in the usual manner and then heated to 170 and 1 g. carefully dehydrated zinc nitratein 100 g. dry commercial ethyl acetate, contaming approximately 85 per cent'of actual ethyl acetate and 15 per cent of ethyl a1cohol, 1s allowed to flow slowly into a 1000 cc. flask, provided with stirrer and reflux condenser and set in an ice-water bath, while 400 cc. dry, freshly distilled acetaldehyde is also being admitted to the flask. Stirring is maintained and the temperature is not allowed to rise appreciably above 20 C. \Vithin a few minutes after the last of the aldehyde and promoter catalyst solutions have been introduced, the reaction subsidesl In one such experiment, we found less than 6 per cent of the original aldehyde not converted into ethyl acetate. In another experiment in which aluminum ethoxide alone was used as the catalyst without any zinc nitrate, fully 25 per cent of the aldehyde was left unconverted at the end of the test. I

We have given this detailed example by way of illustration only. We may vary many of the conditions without departing from the a invention. Thus we may use as the catalyst some other metal alkyl oxide, such as the ethoxide, isopropoxide, or butoxide of titanium or aluminum, and as the aldehyde propionic aldehyde, butyric aldehyde or a mixture of two different aldehydes, such as butyric aldehydeand acetaldehyde, in order to produce butyl acetate. Also, we may vary the proportions of theseveral ingredients, the method of introduction into the reacting vessel, the type of PROCESS OF ESTERIFYING ALDEIEYDES.

Application filed March 26, 1928. Serial No. 264,954.

consists in using a promoter comprising the 1nitrate of a metal whose hydroxide is a weak ase.

2. In the process of converting an aldehyde to an ester in the presence of an alkyl oxide of a trivalent metal, the improvement which consists in using a promoter comprising the nitrate of a metal whose hydroxide is a weak base, said nitrate being soluble in commercial, 85% ethylacetate.

3. In the process of converting an aldehyde to an ester in the presence of an alkyl oxide of a trivalent metal, the improvement which coniistts in using a promoter comprising zinc nira e.

4. In the irocess of converting acetaldehyde to ethyl acetate in the presence of an alkyl oxide of a trivalent metal, the improvement which consists in using a promoter comprising the nitrate of a metal whose hydroxide is a weak base;

5. In the process of converting acetaldehyde to ethyl acetate in the presence of an alkyl oxide of a trivalent metal, the improvement which consists in usin a promoter com-- is a weak base, said nitrate being soluble in commercial, 85% ethyl acetate.

6. In the process of converting acetaldehyde to ethyl acetate in the presence of an alkyl oxide of a trivalent metal, the improvement which consists in using a promoter comprising zinc nitrate.

7. In the process of converting an aldehyde to an ester in the presence of aluminum .ethoxide, the improvement which consists in using a promoter comprising the nitrate of a metal'whose hydroxide is a weak base.

8. In the process of converting an aldehyde to an ester in the presence of aluminum,

\ ethoxide, the improvement which consists in using a promoter comprising the nitrate of a metal whose hydroxide is a weak base, said nitrate being soluble in commercial, 85% ethyl acetate. I

9. In the process of converting an aldehyde to an ester in the presence of aluminum ethoxide, the improvement which consists in using a promoter comprising zinc nitrate.

10.-The process "of converting acetaldehyde to ethyl acetate which comprises the use of aluminum ethoxide and anhydrous zinc nitrate.

11. The process of esterifying acetaldehyde in the presence of a solution of approximately 9 parts by weight of aluminum ethoxide to 1 part of zinc nitrate.

12. The process of esterifying acetaldehyde in the presence of a solution of approximately 9 parts by weight of aluminum ethoxide to 1 part of zinc nitrate at a temperature not substantially above 20 C.

13. The process of converting acetalde hyde to ethyl acetatewhich comprises treatment with aluminum ethoxide that has been heated to approximately 170 C. and then dissolved, along With approximately one-ninth its weight of zinc nitrate, in ethyl acetate.

14. The process of converting an aldeh dc to an ester which comprises the use of an et iyl acetate solution of aluminum ethoxide and zinc nitrate.

15. In the process of converting an aldehyde to an ester, in the presence of an alkyl oxide of a metal, the improvement which consists in using a promoter comprising zinc nitrate.

, 16. In the process of converting an aldehyde to an ester, in the presence of an alkyl oxide of a metal, the improvement which consists in using a promoter comprising a nitrate of a metal whose hydroxide is a weak base.

17. In the process of converting an aldehyde to an ester, in the presence of an alkyl oxide of a metal whose hydroxide is amphoteric, the improvement which consists in using a promoter comprising zinc nitrate.

18. In the process of converting an aldehyde to an ester, in the presence of an alkyl oxide of a metal whose hydroxide is amphoteric, the improvement which consists in using a promoter comprising a nitrate of a metal whose hydroxide is a weak base.

JACQUES SCIIALOH. JOHN w. OLSON. I 

